Ionic liquids (ILs) are a new class of organic solvents that are stable over a large range of temperatures and have negligible vapor pressures.[1] Owing to their molecular structure, associating a cation and an anion, their physicochemical properties can be easily modulated by changing one of the ions. Ionic liquids are now widely used in organic synthesis and chemical separations due to their high solvation ability and their tuneable nature. [2,3] Almost unexplored, surfactant organization in ILs could open new research directions towards micellar catalysis into IL media, solvation enhancement for apolar entities and lyotropic properties. Indeed, surfactant organization occurs in some nonaqueous solvents [4,5] and is largely used in aqueous systems for drug vectorization, catalysis, gelification and other applications.[5] Recently, microemulsions have been obtained in IL-oil mixtures [6] and only premicellar aggregation has been detected in pure ILs. [7,8] However, no clear demonstration of the existence of a micellar phase in ILs has been reported yet.Here, we describe the behavior of a series of pure alkyl poly-(oxyethyleneglycol) ethers in 1-butyl-3-methyl-imidazolium (bmim) ILs with various counter ions [BF 4 À , PF 6 À and Tf 2 N À , that is, bis(trifluoromethylsulfonyl)amide; Figure 1]. The choice of nonionic surfactants, denoted C n E m (n = 12-16; m = 4-8), was justified to avoid the exchange of counter ions with the solvent. For high concentrations of surfactant (ca. 1 mol L À1 ), the mixtures C n E m /bmimBF 4 were generally solid at room temperature with a cloud point at high temperature (see Supporting Information). Herein, all experiments were performed at 25 8C with concentrations lower than 1 mol L À1, at which the mixtures were all limpid and homogeneous.Surface tension measurements were performed to probe the aggregation behavior of the surfactants in bmimBF 4 . For all the selected surfactants, the surface tension of the C n E m /bmimBF 4 solutions decreased when the surfactant concentration increased (Figure 2). This indicated their adsorption at the air/solution interface. The Szyszowski-Langmuir adsorption equation [9] fitted well this decrease, leading to an estimation of the area per molecule of the surfactant at the air/bmimBF 4 interface, that occurred to be comparable or lower than the ones found at the air/water interface (Table 1). Those differences between bmimBF 4 and water may be related to a change in the organization and/or solvation state of the adsorbed surfactants. In bmimBF 4 like in water, the molecular area of the surfactant decreased with increasing alkyl chain length or decreasing number of oxyethylene groups.This initial decrease of the surface tension is followed by an abrupt change in the slope of the surface tension versus C (Figure 3; semi-log plot). After this breaking point, the surface tension of the solutions remains more or less constant. Such a behavior suggested the formation of micelles within the ILs, where the break point corresponds to a critical micelle...

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Natural anisotropic building-blocks such as cellulose nanocrystals (CNCs) have attracted considerable attention due to their biodegradability and nanometer-size. In this work the colloidal behavior of CNCs, obtained from sulfuric acid hydrolysis of microcrystalline cellulose, has been studied in presence of salts of different valences. The influence on the colloidal stability and nature of aggregates has been investigated for monovalent salts (LiCl, NaCl, KCl, CsCl), divalent salts (CaCl 2 and MgCl 2 ), and a trivalent salt (AlCl 3 ), both experimentally by means of turbidity and small angle X-ray scattering (SAXS) measurements, as well as by Monte Carlo simulations using a simple coarse-grained model. For the entire salt series, a critical aggregation concentration (CAC) could be determined by turbidity measurements, as a result of the reduction of effective Coulomb repulsions due to the presence of sulfate groups on the CNC surface. The CACs also followed the Schulze-Hardy law, i.e. the critical aggregation concentration decreased with increasing counterion valence. For the monovalent ions, the CACs followed the trend, which could be rationalized in terms of matching affinities between the cation and the sulfate groups present at the surface of CNCs. From the SAXS measurements it was shown that the density of the aggregates increased with increasing salt concentration and ion valence. In addition, these findings were rationalized by means of simulation, which showed a good correlation with experimental data. The combination of the experimental techniques and the simulations offered insight into interactionaggregation relationship of CNC suspensions, which is of importance for their structural design applications.Electronic supplementary material The online version of this article

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Self-assembly in solution and adsorption at the air-water interface and at solid surfaces were investigated for two amino-acid-based surfactants with conductimetry, NMR, tensiometry, quartz crystal microbalance with monitoring of the dissipation (QCM-D), and surface plasmon resonance (SPR). The surfactants studied were sodium N-lauroylglycinate and sodium N-lauroylsarcosinate, differing only in a methyl group on the amide nitrogen for the sarcosinate. Thus, the glycinate but not the sarcosinate surfactant is capable of forming intermolecular hydrogen bonds via the amide group. It was found that the amide bond, N-methylated or not, gave a substantial contribution to the hydrophilicity of the amphiphile. The ability to form intermolecular hydrogen bonds led to tighter packing at the air-water interface and at a hydrophobic surface. It also increased the tendency for precipitation as an acid-soap pair on addition of acid. Adsorption of the surfactants at a gold surface was also investigated and gave unexpected results. The sarcosine-based surfactant seemed to give bilayer adsorption, while the glycine derivative adsorbed as a monolayer.

The inherent flammability of cellulosic fibers limits their use in some advanced applications. This work demonstrates for the first time the production of flame-retardant macroscopic fibers from wood-derived cellulose nanofibrils (CNF) and silica nanoparticles (SNP). The fibers are made by extrusion of aqueous suspensions of anionic CNF into a coagulation bath of cationic SNP at an acidic pH. As a result, the fibers with a CNF core and a SNP thin shell are produced through interfacial complexation. Silica-modified nanocellulose fibers with a diameter of ca. 15 μm, a titer of ca. 3 dtex and a tenacity of ca. 13 cN tex are shown. The flame retardancy of the fibers is demonstrated, which is attributed to the capacity of SNP to promote char forming and heat insulation on the fiber surface.

Nanostructured fluids containing anionic surfactants are among the best performing systems for the cleaning of works of art. Though efficient, their application may result in the formation of a precipitate, due to the combination with divalent cations that might leach out from the artifact. We propose here two new aqueous formulations based on nonionic surfactants, which are non-toxic, readily biodegradable and insensitive to the presence of divalent ions. The cleaning properties of water-nonionic surfactant-2-butanone (MEK) were assessed both on model surfaces and on a XIII century fresco that could not be cleaned using conventional methods. Structural information on nanofluids has been gathered by means of small-angle neutron scattering, dynamic light scattering and nuclear magnetic resonance with diffusion monitoring. Beside the above-mentioned advantages, these formulations turned out to be considerably more efficient in the removal of polymer coatings than those based on anionic surfactants. Our results indicate that the cleaning process most likely consists of two steps: initially, the polymer film is swollen by the MEK dissolved in the continuous domain of the nanofluid; in the second stage, surfactant aggregates come into play by promoting the removal of the polymer film with a detergency-like mechanism. The efficiency can be tuned by the composition and nature of amphiphiles and is promoted by working as close as possible to the cloud point of the formulation, where the second step proceeds at maximum rate.